Flame-retardant resin composition, prepreg, resin sheet, and molding

ABSTRACT

Provided is a flame-retardant resin composition that keeps flame-retardancy certainly without containing any halogen compound, which may cause the generation of a harmful material, and can simultaneously maintain the original property of the resin at a high level. 
     The invention relates to a flame-retardant resin composition. The composition contains a resin containing any one or both of a thermosetting resin and a thermoplastic resin, and a cyclophosphazene represented by the following formula (1) wherein the cyclophosphazene compound is incorporated into the resin in an amount of 0.1 to 200 parts by mass based on 100 parts by mass of the resin: 
     
       
         
         
             
             
         
       
     
     wherein n=3 to 25, one of R1 and R2 is CN, and the other is H, or both thereof are CN, and the percentage of the cyanophenoxy groups in the compound is from 2 to 98% of the total number of the phenoxy groups and the cyanophenoxy groups in the compound.

TECHNICAL FIELD

The present invention relates to a flame-retardant resin compositionused to produce a printed wiring board or seal (or encapsulate) asemiconductor element; a prepreg and a resin sheet which can each beproduced by use of this flame-retardant resin composition; and a moldingsuch as a printed wiring board or a molding obtained by sealing asemiconductor element.

BACKGROUND ART

Moldings such as a printed wiring board, or moldings obtained by sealinga semiconductor element require flame-retardant in order to ensure thesafety thereof. To make the products flame-retardant can be attained byuse of a resin composition which contains a halogen compound. In recentyears, however, it has been pointed out as a problem that these moldingseach made of the resin composition generate harmful dioxins when theproducts are incinerated.

Thus, instead of using any halogen compound, a compound made mainly ofnitrogen or phosphorus is incorporated, as a flame retardant, into aresin composition, thereby making the composition flame-retardant (see,for example, Patent Documents 1 to 3).

Patent Document 1: JP-A-10-259292

Patent Document 2: JP-A-11-181429

Patent Document 3: JP-A-2002-114981

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

However, the flame-retardant-containing resin compositions described inPatent Documents 1 to 3 are each a compatible system; therefore, afterthe composition is formed into a shape, the original property of theresin may be damaged by the flame retardant. Specifically, by use of theflame retardant, the glass transition temperature (Tg) of the resin islowered so that the heat resistance of the molding may be damaged.

In light of the above-mentioned points, the invention has been made. Anobject of the invention is to provide a flame-retardant resincomposition, a prepreg, a resin sheet and a molding which keepflame-retardancy certainly without containing any halogen compound,which may cause the generation of a harmful material, and cansimultaneously maintain the original property of the resin at a highlevel.

Means for Solving the Problems

A flame-retardant resin composition of the invention according to claim1, wherein the composition includes a resin including any one or both ofa thermosetting resin and a thermoplastic resin, and a cyclophosphazenerepresented by the following formula (1), wherein the cyclophosphazenecompound is incorporated into the resin in an amount of 0.1 to 200 partsby mass based on 100 parts by mass of the resin:

wherein n=3 to 25, one of R1 and R2 is CN, and the other is H, or boththereof are CN, and the percentage of the cyanophenoxy groups in thecompound is from 2 to 98% of the total number of the phenoxy groups andthe cyanophenoxy groups in the compound.

The invention according to claim 2, wherein the composition includes aninorganic filler in claim 1.

The invention according to claim 3, wherein the composition includes oneor more resins selected from the thermosetting resins consisting of agroup of-epoxy resin, radical polymerizable resin, polyimide resin, andmodified resins thereof; and thermoplastic resins consisting of a groupof polyphenylene ether resin, thermoplastic polyimide resin,polyetherimide resin, poyethersulfone resin, phenoxy resin, and modifiedresins thereof.

A prepreg of the invention according to claim 4, wherein the prepreg isobtained by impregnating a glass substrate or an organic fiber substratewith the flame-retardant resin composition as recited in any one ofclaims 1 to 3, and then drying the resultant.

A resin sheet of the invention according to claim 5, wherein the resinsheet is obtained by applying the flame-retardant resin composition asrecited in any one of claims 1 to 3 on a metal foil surface or a filmsurface, and then drying the resultant.

A molding of the invention according to claim 6, wherein the molding isobtained by forming the flame-retardant resin composition as recited inany one of claims 1 to 3 into a shape.

Effect of the Invention

According to the flame-retardant resin composition of the invention ofclaim 1, provided is a composition which can keep flame retardancycertainly by effect of the given cyclophosphazene compound whilemaintaining the original property of the resin at a high level withoutcontaining any halogen compound, which may cause the generation of aharmful material.

According to the invention of claim 2, a molding having an improvedstrength and a further improved flame retardancy can be given.

According to the invention of claim 3, the Tg is made higher comparedwith the use of any other resin, so that a high heat resistance can beobtained.

According to the prepreg of the invention of claim 4, provided is aprepreg which can keep flame retardancy certainly by effect of the givencyclophosphazene compound while maintaining the original property of theresin at a high level without containing any halogen compound, which maycause the generation of a harmful material.

According to the resin sheet of the invention of claim 5, provided is aresin sheet which can keep flame retardancy certainly by effect of thegiven cyclophosphazene compound while maintaining the original propertyof the resin at a high level without containing any halogen compound,which may cause the generation of a harmful material.

According to the molding of the invention of claim 6, provided is amolding which can keep flame retardancy certainly by effect of the givencyclophosphazene compound while maintaining the original property of theresin at a high level without containing any halogen compound, which maycause the generation of a harmful material.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the invention will be described hereinafter.

The flame-retardant resin composition according to the invention can beproduced by incorporating 0.1 to 200 parts by mass of a cyclophosphazenerepresented by a formula (1) illustrated below (hereinafterappropriately referred to as a “cyclophosphazene compound of the formula(1)”) based on 100 parts by mass of a resin including any one or both ofa thermosetting resin and a thermoplastic resin. In the invention, thecyclophosphazene compound of the formula (1) is used as a flameretardant. This cyclophosphazene compound of the formula (1) may be acyclophosphazene compound synthesized by the method described in PatentDocument 3 (JP-A-2002-114981) described above. If the amount of thecyclophosphazene compound of the formula (1) is less than 0.1 part bymass based on 100 parts by mass of the resin, a sufficient flameretardancy cannot be certainly kept. Conversely, if the amount is morethan 200 parts by mass, the amount of the resin is relatively small sothat the composition cannot be formed into a shape. As far as theadvantageous effect based on the cyclophosphazene compound of theformula (1) is not damaged, aluminum hydroxide, silicon dioxide (SiO₂)or the like may be used in combination.

wherein n=3 to 25, one of R1 and R2 is CN, and the other is H, or boththereof are CN, and the percentage of the cyanophenoxy groups in thecompound is from 2 to 98% of the total number of the phenoxy groups andthe cyanophenoxy groups in the compound.

The cyanophenoxy group is a functional group represented by a formula(2) illustrated below, and the phenoxy group is a functional grouprepresented by a formula (3) illustrated below. If the percentage of thecyanophenoxy groups in the cyclophosphazene compound of the formula (1)is less than 2% or is reversely more than 98%, a high flame retardancyand a high glass transition temperature (Tg) cannot be made consistentwith each other.

Specific examples of the cyclophosphazene compound of the formula (1)include as follows:

The percentage of the cyanophenoxy groups can be calculated out bysubstituting the mole numbers of cyanophenol and phenol charged when thecyclophosphazene compound of the formula (1) is synthesized for thefollowing equation:

Percentage (%) of the cyanophenoxy groups=(mole number ofcyanophenol)/(mole number of cyanophenol+mole number of phenol)×100

For reference, in a cyclophosphazene compound represented by a formula(8) illustrated below, no phenoxy group is present and groups or atomsbonded to the P atom are only cyanophenoxy groups except N atoms. Forthis reason, the percentage of the cyanophenoxy groups is 100%. Thus, asufficient flame retardancy cannot be certainly kept as described above.

Examples of the thermosetting resin that may be used include such asmodified polyphenylene ether resin (PPE), polyfunctional epoxy resin,o-cresol novolak epoxy resin, bisphenol A (Bis-A) epoxy resin,triallylisocyanurate resin (TAIC), and bismaleimide resin. In order tomake the Tg high and to make the heat resistance higher, it is preferredto select one or more from the group of epoxy resin, radicalpolymerizable resin, polyimide resin, and modified resins thereof, anduse. Specific examples of the epoxy resin include such as polyfunctionalepoxy resins of triphenylmethane type or the like, o-cresol novolakepoxy resin, and bisphenol A (Bis-A) epoxy resin. Specific examples ofthe radical polymerizable resin include such as methacrylates oracrylates of the above-mentioned epoxy resins, acrylic acid esters, andtriallylisocyanurate resin (TAIC). Specific examples of the polyimideresin include such as bismaleimide resin.

Examples of the thermoplastic resin include such as OH-modifiedpolyphenylene ether resin (PPE), phenoxy resin, polyethersulfone resin(PES), polyphenylene ether resin (PPE), polyimide resin, and styrenebased polymer (SPS) having a syndiotactic structure. In order to makethe Tg high and to make the heat resistance higher, it is preferred toselect one or more from the group of polyphenylene ether resin (PPE),thermoplastic polyimide resin, polyetherimide resin, polyethersulfoneresin (PES), phenoxy resin, and modified resins thereof, and use.Specific examples of the polyphenylene ether resin (PPE) include such asOH-modified polyphenylene ether resin (PPE).

A curing agent or a catalyst may be incorporated into theflame-retardant resin composition according to the invention. Examplesof the curing agent or catalyst that may be used include such asdicyandiamide (DICY), phenol novolak, diaminodiphenylmethane (DDM),2-ethyl-4-methylimidazole (2E4MZ), cumene hydroperoxide (CHP),a,a′-bis(t-butylperoxy-m-isopropyl)benzene, and triphenylphosphine.

The flame-retardant resin composition according to the invention maycontain an inorganic filler in order to enhance the strength of themolding and further enhance the flame retardancy. Examples of theinorganic filler that may be used include such as titania (TiO₂), andcalcium carbonate (CaCO₃). Such an inorganic filler may be incorporatedin an amount of 0.1 to 200 parts by mass based on 100 parts by mass ofthe resin including any one or both of a thermosetting resin and athermoplastic resin. The flame-retardant resin composition according tothe invention may contain, besides the inorganic filler, “CTBN”manufactured by Ube Industries, Ltd., which is a liquid polybutadienerubber having a modified carboxyl terminal, a coupling agent such as

γ-glycidoxypropyltriethoxysilane, a releasing agent such as carnaubawax, and the like.

The flame-retardant resin composition according to the invention can beproduced by incorporating a cyclophosphazene compound of the formula (1)in an amount of 0.1 to 200 parts by mass based on 100 parts by mass ofthe resin including any one or both of a thermosetting resin and athermoplastic resin, and optionally incorporating an inorganic fillerand the like.

The prepreg according to the invention can be produced as follows:First, the above-mentioned flame-retardant resin composition isdissolved in a solvent such as dimethylacetoamide, dimethylformamide(DMF), N-methylpyrrolidone, dimethylsulfoxide, methyl ethyl ketone(MEK), cyclohexanone, toluene or xylene, thereby preparing a vanish.Next, a glass substrate or an organic fiber substrate made of such asaramide fiber, polyester fiber, polyimide fiber, polyacryl fiber isimpregnated with the thus-obtained varnish. Thereafter, this is dried tobe a semi-cured B stage state. In this way, the prepreg according to theinvention can be produced. The thus-obtained prepreg may be used as amaterial of a printed wiring board.

The resin sheet according to the invention can be produced as follows:the sheet can be produced by applying a vanish obtained as describedabove onto a metal foil surface or film surface, and then drying theresultant to be a semi-cured B stage state. The thus-obtained resinsheet may also be used as a material of a printed wiring board.

The resin sheet according to the invention is a sheet obtained as ametal-foil-attached resin sheet in a case of applying the vanish to ametal foil. The resin sheet is a sheet obtained as a film-attached resinsheet in a case of applying the vanish to a film. The metal foil thatmay be used is, for example, copper foil or aluminum foil, and the filmthat may be used is, for example, a fluorine-contained resin film or aPET film.

The molding according to the invention can be obtained by forming theflame-retardant resin composition into a shape. For example, when theflame-retardant resin composition is used as a sealing (orencapsulating) material and this is used to seal and mold asemiconductor element, a semiconductor device can be obtained as amolding.

Since the flame-retardant resin composition according to the inventionis not a compatible system but an incompatible system, the originalproperty of the resin is not damaged by the cyclophosphazene compound ofthe formula (1) after the composition is formed into a shape.Specifically, the use of the cyclophosphazene compound of the formula(1) makes it possible to prevent a fall in the Tg of the thermosettingresin or the thermoplastic resin and heighten the heat resistance of amolding obtained by forming the flame-retardant resin composition into ashape. Since the molding does not have any halogen compound at all,harmful materials such as dioxins are not generated even if the moldingis incinerated. Thus, a nonpoisonous molding can be obtained.

EXAMPLES

The invention will be specifically described by way of the followingexamples.

(Thermoplastic Resins)

As thermoplastic resins, OH-modified PPE-1; OH-modified PPE-2; a phenoxyresin (“PKFE”, manufactured by Inchem); a PES (“POLYETHERSULFONE 5003P”,manufactured by Sumitomo Chemical Co., Ltd.); a PPE (“640-111”,manufactured by Nippon G.E. Plastic Kabushiki Kaisha [transliteration]);a polyimide resin (“ULTEM [transliteration]”, manufactured by NipponG.E. Plastic Kabushiki Kaisha); and an SPS (“33EX003”, manufactured byIdemitsu Petrochemical Co., Ltd.) were used.

OH-modified PPE-1 described above was prepared as follows: that is, to100 parts by mass of toluene were added 100 parts by mass of “640-111”(number-average molecular weight Mn=20000) manufactured by Nippon G.E.Plastic Kabushiki Kaisha, which is a polymer PPE, 5 parts by mass ofbenzoyl peroxide, and 6 parts by mass of bisphenol A. This was stirredat 60° C. for 90 minutes to conduct redistribution reaction, therebyyielding a solution of OH-modified PPE-1. The molecular weightdistribution of OH-modified PPE-1 in this solution was measured by gelpermeation chromatography (column structure: “SuperHM-M” (singlecolumn)+“SuperHM-H” (single column) manufactured by Tosoh Corp.). As aresult, it was confirmed that the number-average molecular weight ofOH-modified PPE-1 was 2300.

OH-modified PPE-2 described above was prepared in the same way asOH-modified PPE-1 except that 3 parts by mass of bisphenol A was added.The molecular weight distribution of OH-modified PPE-2 was measured inthe same way as that of OH-modified PPE-1. As a result, it was turnedout that the number-average molecular weight of OH-modified PPE-2 was4000.

(Thermosetting Resins)

As thermosetting resins, a modified PPE; a polyfunctional epoxy resin(“EPPN501H”, manufactured by Nippon Kayaku Co., Ltd.; an o-cresolnovolak epoxy resin (“EOCN195XL4”, manufactured by Sumitomo ChemicalCo., Ltd.); a Bis-A methacrylate resin; a TAIC (manufactured by NipponKasei Chemical Co., Ltd.); and a bismaleimide resin (“BMI-S”,manufactured by Daiwa Kasei K.K.) were used.

The modified PPE was prepared as follows: first, mixed were 36 parts bymass of “NOLYL [transliteration] PX9701” (number-average molecularweight Mn=14000) manufactured by Nippon G.E. Plastic Kabushiki Kaisha,which is a PPE, 0.77 part by mass of 2,6-xylenol, which is a kind ofphenol, 1.06 parts by mass of t-butylperoxyisopropylmonocarbonate(“PERBUTYL I”, manufactured by NOF Corp.) as an initiator, and 0.0015part by mass of cobalt naphthenate. 90 parts by mass of toluene wasadded thereto as a solvent. The components were mixed with each other at80° C. for 1 hour to disperse and dissolve the components and cause thereaction. In this way, a PPE solution was obtained. The molecular weightdistribution of the PPE in this solution was measured by gel permeationchromatography (column structure: “SuperHM-M” (singlecolumn)+“SuperHM-H” (single column) manufactured by Tosoh Corp.). As aresult, it was confirmed that the number-average molecular weight of thePPE was about 3500. The PPE solution was dried at 70° C. under reducedpressure to remove toluene as a solvent until the concentration thereofto be 1% or less by mass. Next, allyl groups (CH₂═CH—CH₂—), which areeach an unsaturated group of carbon-carbon, were introduced into themolecules of the PPE, the molecular weight of which was lowered asdescribed above. Specifically, the PPE was weighed out in an amount of350 g. This was dissolved in 7 liters of tetrahydrofuran, and furtherthereto was added 390 mL of a solution of n-butyllithium in hexane (1.5moles/liter). The resultant solution was stirred at 40° C. for 1 hour tocause the reaction. To this reactant was added 30 mL of allylbromide,and further the solution was stirred for 30 minutes while thetemperature was kept at 40° C. To this solution was added a mixedsolvent of 3 L of water and 3 L of methanol to precipitate a polymer.Filtration and washing with methanol were repeated 5 times. Thereafter,the resultant was vacuum-dried at 50° C. for 24 hours to yield amodified PPE as an allyl-group-containing PPE.

The Bis-A methacrylate resin was prepared as follows: Into a four-neckedflask were charged 136 g of “YD-128” (epoxy equivalent: 190)manufactured by Tohto Kasei Co., Ltd. as an epoxy resin, 0.4 g oftriphenylphosphine, 0.06 g of hydroquinone, and 0.21 g of methacrylicacid. Thereafter, the reactive components were caused to react at 120°C. until the acid value turned to 10.0 or less. Next, thereto werecharged 90 g of styrene and 12 g of acrylic acid, so as to yield theBiS-A methacrylate resin as a radical polymerizable resin.

(Flame Retardants)

As flame retardants, the following were used: incompatible typephosphazenes 1 to 5 having cyanophenoxy groups; a compatible typephosphazene (“SPB100”, manufactured by Ohtsuka Chemical Industrial Co.,Ltd.); aluminum hydroxide; and silicon oxide (SiO₂).

Incompatible type phosphazenes 1 to 5 having cyanophenoxy groups(corresponding to Synthesis Examples 1 to 5 in Table 1 described below,respectively) were synthesized as follows: To a four-necked flask havinga volume of 2 liters and equipped with a stirrer, a heater, athermometer and a dehydrator were added 1.76 moles of 4-cyanophenol,0.88 mole of phenol, 2.64 moles of sodium hydroxide, and 1000 mL oftoluene. Next, this mixture was heated and refluxed to remove water fromthe system to prepare a toluene solution containing a sodium salt ofcyanophenol and a sodium salt of phenol. To this toluene solution of thesodium salts of cyanophenol and phenol was dropwise added 580 g of a 20%solution containing one mole of dichlorophosphazene oligomer 1(containing trimers in an amount of 95% or more) in chlorobenzene at aninternal temperature of 30° C. or lower while the former solution wasstirred. This mixed solution was refluxed for 12 hours, and then a 5%sodium hydroxide solution in water was added to the reaction mixture soas to wash the mixture two times. Next, the organic phase wasneutralized with diluted sulfuric acid, and then washed with water 2times. The organic phase was filtrated, concentrated, and vacuum-dried(conditions for the vacuum-drying: 80° C. and 5 mmHg for 12 hours),thereby yielding incompatible type phosphazene 1 having cyanophenoxygroups (Synthesis Example 1). This was identified as“N=P(OC₆H₄CN)_(1.34)(OC₆H₅)_(0.66)” by elementary analysis.

Incompatible type phosphazene 2 containing cyanophenoxy groups(Synthesis Example 2) was synthesized in the same way as in SynthesisExample 1 except that instead of dichlorophosphazene oligomer 1,dichlorophosphazene oligomer 2 (containing trimers in an amount of 85%or more and containing the trimers and tetramers in a total amount of95% or more) was used.

Incompatible type phosphazenes 3 to 5 containing cyanophenoxy groups(Synthesis Examples 3 to 5) were each synthesized in the same way as inSynthesis Example 1 except that the mole number of 4-cyanophenol andthat of phenol were changed as shown in Table 1 described below.

TABLE 1 Synthesis Synthesis Synthesis Synthesis Synthesis Example 1Example 2 Example 3 Example 4 Example 5 Dichlorophosphazene oligomer 1(*) 115.9 (1)    0 115.9 (1)   115.9 (1)    115.9 (1)   mass (mole(s))Dichlorophosphazene oligomer 2 (#) 0 115.9 (1)    0 0 0 mass (mole(s))4-Cyanophenol mass (moles) 209.6 (1.76)  209.6 (1.76)  157.2 (1.32) 262(2.2)  314.4 (2.64) Phenol mass (mole(s)) 82.8 (0.88) 82.8 (0.88) 124.2(1.32) 52.4 (0.44) 0 Percentage of cyanophenol groups 67% 67% 50% 83%100% (*) Oligomer containing trimers in an amount of 95% or more (#)Oligomer containing trimers in an amount of 85% or more and the trimersand tetramers in a total amount of 95% or more)

(Curing Agents/Catalysts)

As curing agents or catalysts, dicyandiamide (DICY); a phenol novolak(“H-4”, manufactured by Meiwa Chemical Industry Co., Ltd.);diaminodiphenylmethane (manufactured by Sumitomo Chemical Co., Ltd.);2-ethyl-4-methylimidazole (2E4MZ) (manufactured by Shikoku ChemicalsCorp.); cumene hydroperoxide (CHP) (“PERCUMIL [transliteration] H-80”,manufactured by NOF Corp.);

a,a′bis(t-butylperoxy-m-isopropyl)benzene (“PERBUTYL P”, manufactured byNOF Corp.); and triphenylphosphine (reagent manufactured by Wako PureChemical Industries, Ltd.) were used.

(Other Additives)

As other additives, CTBN (“Highcker [transliteration] CTBN 1300×13”,manufactured by Ube Industries, Ltd.); γ-glycidoxypropyltriethoxysilane;carnauba wax; titania; and calcium carbonate were used.

(Varnishes)

With respect to each of Examples 1 to 5 and 13 to 19, and ComparativeExamples 1 to 4 and 9 to 11, individual components were blended in blendamounts (part(s) by mass) shown in Table 2, 4, 5, 6, 7, or 8 describedbelow. The resultant was diluted with toluene to be the solid content inpercentage of 50% by mass, thereby yielding a vanish for impregnation.

With respect to each of Example 6 and Comparative Example 5, individualcomponents were blended in blend amounts (part(s) by mass) shown inTable 2 or 6 described below. The resultant was diluted with a mixedsolvent of DMF/MEK/methoxypropanol (ratio by mass=23/12/15) to be thesolid content in percentage of 50% by mass, thereby yielding a vanishfor impregnation.

With respect to Example 7, individual components were blended in blendamounts (part(s) by mass) shown in Table 2 described below. Theresultant was diluted with MEK to be the solid content in percentage of50% by mass, thereby yielding a vanish for impregnation.

With respect to each of Examples 8 and 9 and Comparative Example 6,individual components were blended in blend amounts (part(s) by mass)shown in Table 3 or 7 described below. The resultant was diluted withstyrene monomers to be the solid content in percentage of 70% by mass,thereby yielding a vanish for impregnation.

With respect to each of Example 10 and Comparative Example 7, individualcomponents were blended in blend amounts (part(s) by mass) shown inTable 3 or 7 described below. The resultant was diluted with DMF to bethe solid content in percentage of50% by mass, thereby yielding a vanishfor impregnation.

With respect to each of Examples 11 and 12 and Comparative Example 8,individual components were blended in blend amounts (part(s) by mass)shown in Table 3 or 7 described below. The resultant was diluted with amixed solvent of

DMF/MEK/methoxypropanol (ratio by mass=23/12/15) to be the solid contentin percentage of 50% by mass, thereby yielding a vanish forimpregnation.

With respect to each of Example 20 and Comparative Example 12,individual components were blended in blend amounts (part(s) by mass)shown in Table 5 or 8 described below. The resultant was diluted with amixed solvent of

DMF/cyclohexanone/MEK (ratio by mass=20/80/25) to be the solid contentin percentage of 40% by mass, thereby yielding a vanish forimpregnation.

A “HOMODISPER” manufactured by PRIMIX Corp. was used to stir thevarnishes for impregnation and painting at about 1000 rpm for about 90minutes. The above-mentioned solid contents mean each the amount of anycomponent other than the solvent.

(Evaluating Samples)

With respect to each of Examples 1 to 7, 9, 10 and 13 to 20, andComparative Examples 1, 2, 4, 5, 7 and 9 to 12, a laminated plate (CCL)was produced as an evaluating sample. Specifically, a glass cloth(individual weight: 107 g/m², and thickness: 0.1 mm) was impregnatedwith each of the varnishes for impregnation, and the resultant was driedto produce prepregs (resin amount: 40% by mass). Eight out of theprepregs were put onto each other, and further a copper foil piecehaving a thickness of 18 μm was put onto each of the front and rearsurfaces thereof. This was heated and pressed under curing conditionsthat the temperature was 200° C., the pressure was 3 MPa and the periodwas 120 minutes, so as to perform lamination molding, thereby producinga double-sided copper-clad laminated plate (CCL). With respect toComparative Example 3, no evaluating sample was able to be produced.

With respect to each of Example 8 and Comparative Example 6, a compositelaminated plate (CEM3) was produced as an evaluating sample.Specifically, plain woven glass clothes (thickness: 200 μm, and size:300 mm×300 mm) and glass paper pieces (individual weight: 51 g/m²,density: 0.14 g/cm³, and size: 300 mm×300 mm) were impregnated with eachof the vanishes for impregnation to obtain plain woven glass clothimpregnation-products and glass paper piece impregnation-products. Next,two out of the glass paper piece impregnation-products were put ontoeach other, and then one out of the plain woven glass clothimpregnation-products was put and laminated onto each side of theresultant so as to give a sandwich structure. Furthermore, one copperfoil piece having a thickness of 18 μm was put onto each side of theresultant to yield a laminate. This laminate was sandwiched betweenmetal plates, and the resultant workpiece was subjected to laminationmolding under curing conditions that the temperature was 110° C. and theperiod was 30 minutes. Thereafter, the workpiece was after-cured underconditions that the temperature was 180° C. and the period was 30minutes to produce a composite copper-clad laminated plate having athickness of 1.6 mm.

With respect to each of Example 11 and Comparative Example 8, a resinsheet covered with copper foil (RCC) was produced as an evaluatingsample. Specifically, each of the varnishes for painting was paintedonto a roughed surface of a copper foil piece (“GT”, manufactured byFurukawa Circuit Foil Co., Ltd.) having a thickness of 0.018 mm with acomma coater at room temperature. This was heated at about 160° C. bymeans of a noncontact type heating unit to remove the meltable agent inthe vanish and further dry the workpiece into a semi-cured B stagestate, thereby producing a resin sheet covered with the copper foil(RCC) having a resin layer of 80 μm thickness.

With respect to Example 12, a film-covered resin sheet was produced asan evaluating sample. Specifically, a comma coater was used to apply thevanish for applying to a surface of a PET film having a thickness of 40μm to be a thickness of about 60 μm. While this workpiece was carried ata carrying speed of 20 cm/minute, the workpiece was heated at atemperature of 100° C. so as to be dried into a semi-cured B stagestate. Furthermore, in order to protect the vanish-painted surface, apolyethylene film 20 μm in thickness was used as a cover film and thevanish-painted surface was covered with this film to produce afilm-covered resin sheet (thickness of its resin layer: 30 μm).

With respect to each of Example 21 and Comparative Example 13,individual components were blended in blend amounts (part(s) by mass)shown in Table 5 or 8 described below to produce a flame-retardant resincomposition usable as a sealing material. Next, this composition washeated at 175° C. for 90 seconds to be cured, and further thecomposition was after-cured at 175° C. for 6 hours to produce anevaluating sample (test piece).

With respect to each of Example 22 and Comparative Example 14,individual components were blended in blend amounts (part(s) by mass)shown in Table 5 or 8 described below. This blend product was melted andkneaded by means of a heating roll in a temperature from 85 to 95° C.,so as to produce a molding material. This molding material was subjectedto injection molding to produce an evaluating sample (test piece).

(Frame Retardancy (FR Property))

With respect to each of Examples 1 to 10 and 13 to 22, and ComparativeExamples 1, 2, 4 to 7 and 9 to 14, a test piece 125 mm long and 13 mmwide was cut away from the evaluating sample (the CCL, the CEM3, or thetest piece). With respect to this test piece, a burning behavior testwas made in accordance with “Test for Flammability of PlasticMaterials-UL 94”, of Underwrites laboratories.

With respect to each of Example 11 and Comparative Example 8, from acopper-clad laminate plate “R1566” (substrate thickness: 0.8 mm, andcopper foil piece thickness: 18 μm) manufactured by Matsushita ElectricWorks, Ltd., the copper foil was removed by etching, so as to produce acore material. The RCC which was the evaluating sample was put onto eachof the surfaces of this core material in such a manner that the resinside of the RCC was brought into contact with the core material. Theresultant was pressed, and then cured. Next, the outside copper foilpieces were removed from this cured product by etching, and then a testpiece 125 mm long and 13 mm wide was cut away therefrom. With respect tothis test piece, a burning behavior test was made in accordance with“Test for Flammability of Plastic Materials-UL 94” of Underwriteslaboratories.

With respect to Example 12, from a copper-clad laminate plate “R1566”(substrate thickness: 0.8 mm, and copper foil piece thickness: 18 μm)manufactured by Matsushita Electric Works, Ltd., the copper foil wasremoved by etching, so as to produce a core material. The film which wasthe evaluating sample was put onto each of the surfaces of this corematerial. A vacuum laminator manufactured by Meiki Co., Ltd. was used tolaminate the film onto the core material, and then the resultant wascured. Next, a test piece 125 mm long and 13 mm wide was cut away fromthis cured product. With respect to this test piece, a burning behaviortest was made in accordance with “Test for Flammability of PlasticMaterials-UL 94” of Underwrites laboratories.

(Glass Transition Temperature (Tg))

About each of the evaluating samples of Examples 1 to 10 and 13 to 22,and Comparative Examples 1, 2,4 to 7 and 9 to 14, a viscoelasticspectrometer “DMS100” manufactured by Seiko Instruments Ltd. was used tomeasure the glass transition temperature (Tg). At this time, themeasurement was set to be the frequency in a bending module to 10 Hz.When the temperature was raised from room temperature to 280° C. underthe condition that the temperature-raising rate was 5° C./min., thetemperature at which the tanδ showed a maximum value was defined as theglass transition temperature (Tg).

With respect to each of the evaluating samples of Examples 11 and 12,and Comparative Example 8, a viscoelastic spectrometer “DMS200”manufactured by Seiko Instruments Ltd. was used to measure the glasstransition temperature (Tg). At this time, the measurement was made toset the frequency in a tensile module to 10 Hz. When the temperature wasraised from room temperature to 280° C. under the condition that thetemperature-raising rate was 5° C./min., the temperature at which thetans showed a maximum value was defined as the glass transitiontemperature (Tg).

The results of the flame retardancy (FR property) and the measuredresults of the glass transition temperature (Tg) are shown in Tables 2to 8 described below.

TABLE 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6Example 7 Thermoplastic resin OH-modified PPE-1 40 40 40 40 40OH-modified PPE-2 Phenoxy resin PES PPE Polyimide resin SPSThermosetting resin Modified PPE Polyfunctional epoxy resin 58 58 58 5858 94 63 o-Cresol novolak epoxy resin Bis-A methacrylate TAICBismaleimide Curing agent/catalyst DICY 6 Phenol novolak 37 DDM 1 1 1 11 2E4MZ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CHP PERBUTYL P TriphenylphosphineOthers CTBN γ-Glycidoxypropyltriethoxysilane Carnauba wax TitaniaCalcium carbonate Frame retardant Synthesis Example 1 30 15 50 21Synthesis Example 2 30 9 Synthesis Example 3 Synthesis Example 4 30 30Aluminum hydroxide SiO₂ Items Evaluating sample CCL CCL CCL CCL CCL CCLCCL Frame retardancy (FR property) V-0 V-1 V-0 V-0 V-0 V-0 V-0 Glasstransition temperature (Tg) 202 204 202 200 201 170 182

TABLE 3 Example 8 Example 9 Example 10 Example 11 Example 12Thermoplastic resin OH-modified PPE-1 OH-modified PPE-2 Phenoxy resin 1010 PES PPE Polyimide resin SPS Thermosetting resin Modified PPEPolyfunctional epoxy resin 85 85 o-Cresol novolak epoxy resin Bis-Amethacrylate 94 94 TAIC Bismaleimide 78 Curing agent/catalyst DICY 5 5Phenol novolak DDM 22 2E4MZ 0.1 0.1 CHP 1 1 PERBUTYL PTriphenylphosphine Others CTBN 6 6 6 γ-GlycidoxypropyltriethoxysilaneCarnauba wax Titania Calcium carbonate Frame retardant Synthesis Example1 50 50 15 Synthesis Example 2 Synthesis Example 3 Synthesis Example 430 30 Aluminum hydroxide 100 100 SiO₂ Items Evaluating sample CEM3 CCLCCL RCC Film Frame retardancy (FR property) V-0 V-0 V-0 V-0 V-0 Glasstransition temperature (Tg) 174 180 240 168 168

TABLE 4 Example 13 Example 14 Example 15 Example 16 Example 17Thermoplastic resin OH-modified PPE-1 40 40 40 40 OH-modified PPE-2 40Phenoxy resin PES PPE Polyimide resin SPS Thermosetting resin ModifiedPPE Polyfunctional epoxy resin 58 58 58 58 o-Cresol novolak epoxy resinBis-A methacrylate TAIC 60 Bismaleimide Curing agent/catalyst DICYPhenol novolak DDM 1 1 1 1 2E4MZ 0.1 0.1 0.1 0.1 CHP PERBUTYL P 2.5Triphenylphosphine Others CTBN γ-Glycidoxypropyltriethoxysilane Carnaubawax Titania Calcium carbonate Frame retardant Synthesis Example 1 10 1030 Synthesis Example 2 Synthesis Example 3 30 10 10 Synthesis Example 430 10 10 Aluminum hydroxide 35 SiO₂ 30 Items Evaluating sample CCL CCLCCL CCL CCL Frame retardancy (FR property) V-0 V-0 V-0 V-0 V-0 Glasstransition temperature (Tg) 200 198 203 198 196

TABLE 5 Example 18 Example 19 Example 20 Example 21 Example 22Thermoplastic resin OH-modified PPE-1 OH-modified PPE-2 Phenoxy resinPES 21 PPE 30 Polyimide resin SPS 38 Thermosetting resin Modified PPE 70Polyfunctional epoxy resin 50 o-Cresol novolak epoxy resin 9.4 Bis-Amethacrylate TAIC 30 70 70 Bismaleimide Curing agent/catalyst DICYPhenol novolak 29 5.1 DDM 2E4MZ 0.08 CHP PERBUTYL P 2.5 3Triphenylphosphine 0.1 Others CTBN γ-Glycidoxypropyltriethoxysilane 0.30.45 Carnauba wax 0.2 Titania 45 Calcium carbonate 11 Frame retardantSynthesis Example 1 30 30 15 6 Synthesis Example 2 Synthesis Example 3Synthesis Example 4 2.4 Aluminum hydroxide SiO₂ 85 Items Evaluatingsample CCL CCL CCL Sealing molding material material Frame retardancy(FR property) V-0 V-0 V-0 V-0 V-0 Glass transition temperature (Tg) 230170 175 193 100

TABLE 6 Comparative Comparative Comparative Comparative Example 1Example 2 Comparative Example 3 Example 4 Example 5 Thermoplastic resinOH-modified PPE-1 40 40 40 40 OH-modified PPE-2 Phenoxy resin PES PPESPS Polyimide resin Thermosetting resin Modified PPE Polyfunctionalepoxy resin 58 58 58 58 94 o-Cresol novolak epoxy resin Bis-Amethacrylate TAIC Bismaleimide Curing agent/catalyst DICY 6 Phenolnovolak DDM 1 1 1 1 2E4MZ 0.1 0.1 0.1 0.1 0.1 CHP PERBUTYL PTriphenylphosphine Others CTBN γ-Glycidoxypropyltriethoxysilane Carnaubawax Titania Calcium carbonate Frame retardant Compatible typephosphazene 24 24 Synthesis Example 5 30 Synthesis Example 1 230Aluminum hydroxide SiO₂ Items Evaluating sample CCL CCL No sample wasable to CCL CCL be obtained. Frame retardancy (FR property) Total lossby V-0 — V-2 V-0 burning Glass transition temperature (Tg) 202 156 — 200130

TABLE 7 Comparative Comparative Comparative Comparative ComparativeExample 6 Example 7 Example 8 Example 9 Example 10 Thermoplastic resinOH-modified PPE-1 OH-modified PPE-2 40 Phenoxy resin 10 PES PPE SPSPolyimide resin Thermosetting resin Modified PPE 70 Polyfunctional epoxyresin 85 o-Cresol novolak epoxy resin Bis-A methacrylate 94 TAIC 60 30Bismaleimide 78 Curing agent/catalyst DICY 5 Phenol novolak DDM 22 2E4MZ0.1 CHP 1 PERBUTYL P 1 2.5 2.5 Triphenylphosphine Others CTBN 6 6γ-Glycidoxypropyltriethoxysilane Carnauba wax Titania Calcium carbonateFrame retardant Compatible type phosphazene 24 12 24 24 24 SynthesisExample 5 Synthesis Example 1 Aluminum hydroxide 100 SiO₂ 30 ItemsEvaluating sample CEM3 CCL RCC CCL CCL Frame retardancy (FR property)V-0 V-0 V-0 V-0 V-0 Glass transition temperature (Tg) 132 218 127 156189

TABLE 8 Comparative Comparative Comparative Comparative Example 11Example 12 Example 13 Example 14 Thermoplastic resin OH-modified PPE-1OH-modified PPE-2 Phenoxy resin PES 21 PPE 30 SPS 44 Polyimide resinThermosetting resin Modified PPE 50 Polyfunctional epoxy resin o-Cresolnovolak epoxy resin 9.4 Bis-A methacrylate TAIC 70 Bismaleimide Curingagent/catalyst DICY Phenol novolak 29 5.1 DDM 2E4MZ 0.08 CHP PERBUTYL P3 Triphenylphosphine 0.1 Others CTBN γ-Glycidoxypropyltriethoxysilane0.3 Carnauba wax 0.2 Titania 45 Calcium carbonate 11 Frame retardantCompatible type phosphazene 24 12 Synthesis Example 5 Synthesis Example1 Aluminum hydroxide SiO₂ Items Evaluating sample CCL CCL Sealingmaterial molding material Frame retardancy (FR property) V-0 V-0 V-1 V-2Glass transition temperature (Tg) 130 155 193 100

1. A flame-retardant resin composition, comprising a resin comprisingany one or both of a thermosetting resin and a thermoplastic resin, anda cyclophosphazene represented by the following formula (1), wherein thecyclophosphazene compound is incorporated into the resin in an amount of0.1 to 200 parts by mass based on 100 parts by mass of the resin:

wherein n=3 to 25, one of R1 and R2 is CN, and the other is H, or boththereof are CN, and the percentage of the cyanophenoxy groups in thecompound is from 2 to 98% of the total number of the phenoxy groups andthe cyanophenoxy groups in the compound.
 2. The flame-retardant resincomposition according to claim 1, comprising an inorganic filler.
 3. Theflame-retardant resin composition according to claim 1, wherein thecomposition comprises one or more resins selected from the thermosettingresins consisting of a group of epoxy resin, radical polymerizableresin, polyimide resin, and modified resins thereof; and thermoplasticresins consisting of a group of polyphenylene ether resin, thermoplasticpolyimide resin, polyetherimide resin, poyethersulfone resin, phenoxyresin, and modified resins thereof.
 4. A prepreg obtained byimpregnating a glass substrate or an organic fiber substrate with aflame-retardant resin composition according to claim 1, and then dryingthe resultant.
 5. A resin sheet obtained by applying a flame-retardantresin composition according to claim 1 on a metal foil surface or a filmsurface, and then drying the resultant.
 6. A molding obtained by forminga flame-retardant resin composition according to claim 1 into a shape.7. The flame-retardant resin composition according to claim 2, whereinthe composition comprises one or more resins selected from thethermosetting resins consisting of a group of epoxy resin, radicalpolymerizable resin, polyimide resin, and modified resins thereof; andthermoplastic resins consisting of a group of polyphenylene ether resin,thermoplastic polyimide resin, polyetherimide resin, poyethersulfoneresin, phenoxy resin, and modified resins thereof.
 8. A prepreg obtainedby impregnating a glass substrate or an organic fiber substrate with aflame-retardant resin composition according to claim 2, and then dryingthe resultant.
 9. A prepreg obtained by impregnating a glass substrateor an organic fiber substrate with a flame-retardant resin compositionaccording to claim 3, and then drying the resultant.
 10. A prepregobtained by impregnating a glass substrate or an organic fiber substratewith a flame-retardant resin composition according to claim 7, and thendrying the resultant.
 11. A resin sheet obtained by applying aflame-retardant resin composition according to claim 2 on a metal foilsurface or a film surface, and then drying the resultant.
 12. A resinsheet obtained by applying a flame-retardant resin composition accordingto claim 3 on a metal foil surface or a film surface, and then dryingthe resultant.
 13. A resin sheet obtained by applying a flame-retardantresin composition according to claim 7 on a metal foil surface or a filmsurface, and then drying the resultant.
 14. A molding obtained byforming a flame-retardant resin composition according to claim 2 into ashape.
 15. A molding obtained by forming a flame-retardant resincomposition according to claim 3 into a shape.
 16. A molding obtained byforming a flame-retardant resin composition according to claim 7 into ashape.